Trisazo dyestuffs and process of preparing the same



Patented June 13, 1933 TES UNITED STA PATENT OFFICE.

IVAN GUIBELMANN, or scorn MILWAUKEE, AND ARTHUR R. MURPHY, or MILWAUKEE,

wrscousm, ASSIGNORS, BY MESNE ASSIGNMEN COMPANY, A CORPORATION orDELAWARE TRISAZO nYEsruFrs AND rRocEss or rnnramue THE SAME No Drawing.

Thisinvention relates to azo dyestuffs.

It is an object of this invention to produce azo dyestulfs producing oncotton blue, to.

bluish gray to gray shades, of superior fastness to light and to Washingand of good solubility.

i We have found that dyestuffs satisfying these qualifications may beobtained by interchanged.

formula y .diazotizing an aryl-amine containing no hydroxyl groups andcoupling the same to a dialkoxyaniline having the position para to theamino group free, rediazotizing and coupling to Cleves acid or toanother dialkoxyaniline molecule having a free para position,rediazotizing and finally coupling to anacidyl-Q-amino-S-naphthol-G-sulfonic acid compound. If desired, thesequence of the second and third components may be Our novel dyestuifshave the general R1N=N-RzN=NRaN=N NH-COR HOaS wherein R is an arylresidue of the benzene or naphthalene series, preferably containing asulfonic acid group, but containing no hydroxyl groups. R may, however,contain bluish-violet color and in sulfuric acid with greenish-bluecolor. They dye cotton direct ly in blue to bluish-gray to gray shadesof excellent fastness to light. They also .dye silk and regeneratedcellulose fibers.

The following examples will serve further to illustrate our invention,but it should be understood that the same are merely illus- Application.filed November 21, 1930. serial No. 497,328.

TS, TO E. I. DU ."PONT DE NEMOURS & M

trative, not limitative. The parts given are it coupled to153parts of2,5dimethoxy-aniline in the presence of acid. After stirring 12 hoursthe precipitated coupling product I 207.5 parts ofp-chloro-aniline-m-sulfonic" i h a ed to C. and filtered. The resultingproduct is formed into a paste in ice and water, 232 parts of 20 B.hydrochloric acid are added, andthe product is next diazotized by theaddition of 69 parts of sodium nitrite When diazotizationis complete, acold aque-""' ous solution of 223 parts of 1,6-Cleves acid and 53 partsof sodium carbonate areadded to the mass. The coupling is completed byneutralizing the mineral acid with sodium... acetate. The resultingproduct is now converted into the sodium salt by the addition of sodiumhydroxide and is next further diazotized by adding 69 parts of sodiumnitrite and running the mixture into HCl sufiicient, to insure mineralacidity. This compound is next coupled to 281 parts of 2-acetylamin0-8-naphthol-6-sulfonic acid in the presence of sodium carbonate. Thecompleted coupling mass is heated to 70 C. salted out and...

filtered.

As the drypowder, it has a dark appearance with a bronzy luster. It issoluble in water with a bluish-violet color and in concentrated sulfuricacid solution.

On reducing the dye with stannous chloride the following products areobtained, p-chloroaniline-m-sulfonic acid, 2,5-dimethoxy-1,4- phenylenediamine,

1,4-naphthylene dia-v .9

mine-G-sulfonic acid, 2-acetyl-amino-7-amino-8-naphthol-G-sulfonic acid.It dyes cotton in bluish gray shades wit remarkable fastness to lightand good fastness to Washing. On mixed cotton and silk fibers dyed froma neutral Glaubers salt bath, it leaves the silk practically unchangedand the dyeings are discharged to a clear white with hydrosulfite. Itwill, however, dye silk 7 from an acid bath and regenerated cellulosegives a greenish-blue,.5

from a neutral Glaubers salt bath in bluish gray shades.

Example 2 303 parts of Q-naphthylamine-tl, 8-disultonic acid are used inplace of p-chloro-aniline-m-sulfonic acid as used in Example 1 and allotherconditions set out in the example are maintained. A dyestufi havingsimilar properties of the product of Example 1 is obtained.

This dye yields upon reduction 2-naphthylamine-6-8-disulfonic acid,2,5-dimethoXy-1. 4 phenylcne diamine, 1, 1 naphthylenc-di-.nnine-G-sulfonic acid and 2-acetylan1ino-7-amino-S-naphthol-(i-sulfonic acid.

In analogousmanner a great number of other dyestuffs of similar generalproperties may be prepared by replacing the various :omponentsmentionedin Example 1 by their various equivalents as specified at the beginningof this specification. Thus, instead of starting withp-chloro-aniline-meta-sulfonic acid, we may use other halogensubstituted .miline-sulfonic acids and these may be substituted in otherpositions; omor p-anilinesulfonic acid; the various toluidine sulionicacids, anisidine sulfonic acids; the various alpha andbeta-naphthylamine-monoor poly-sulfonic acids; and the like. Instead of2,5-dimethoxy-aniline, other dialkoxy anilines such as2,5-diethoXy-aniline, 2,6-dimethoXy-aniline may be used provided theposition para to the amino group is free.

Instead of coupling first to the dialkoxyaniline and then to Clevesacid, we may couple first to Cleves acid'and then re-diazotize andcouple to the dialkoXy-aniline. We may also use the dialkoXy-aniline asboth second and third component, provided the entire molecule contains asufficient amount of SO H groups to render the same water- .soluble to asatisfactory degree. As Cleves acid, we may use either the 1, 6 or1,7-naphthylamine sulfonic acid, or a mixture of the two. As an acidylgroup in the end component' we may use the formyl residue, acetylresidue, benzoyl residue or the like.

In the claims below it should be understood that where new products,dyestufi's, or articles of manufacture are claimed, we mean to includethose bodies not only in substance, but also in whatever state theyexist when applied'to material dyed, printed, or pigmented therewith.

\Ve are aware that numerous details of the process may be varied througha wide range without departing from the principles of this invention,and we, therefore, do not purpose limiting the patent granted hereonotherwise than necessitated by the prior art. We claim as our invention:

1. The process of preparing azo dyestuffs which comprises diazotizing anaryl-amine of the benzene or naphthalene series having no phenolicgroups, coupling to a component of the group consisting ofdialkoxyaniline having a free para position and Cleves acid,rediazotizing, coupling to the second member of said group or again to.CllllliOXY-flfilllHG, rediazotizing and coupling .(3-siilfoi1ic acid.

The process of preparing an azo dye-" stuff, which. comprisesdiazotizing p-chloroanihne-mcta-sulfon1c acid, coupling to 2,5-diinethoxy-aniline, rediazotizing, coupling to Cleves acid,rediazotizing and coupling to acetyl 2 ammo 8 naphthol-G-sulfomc' acid.

l. In the process of preparing an azo dyestuil, the step which comprisesdiazotizing a compound of the following probable ,gen-

eral formula in which It, is an aryl residue of the benzene ornaphthalene series which contains no hydroxyl groups, and in which oneof the members R and R1, is a dialkoxy-benzene residue while theotherisa naphthalene sulfonic acid residue orrin which both R and R aredialkoxy-benzene residues, and coupling to a compound of the followingprobable general formula in which 1% is an acyl group.

5. In the process of preparing an azo dyestuii', the step whichcomprises diazotizing a compound of the following probable formula:

| $02.11 OCH;

1 I R R in which one B is an 1-1 group while the other R- is a hydrogenatom and coupling'to acetyl-Q-amino-8-naphthol6-sulfonic acid.

. 6. Asnew products of manufacture, dyestuffs having the followinggeneral formula 1 HOaS- wherein R is an aryl residue of the benzene ornaphthalene series which contains no OH groups; wherein one of themembers R and R is a dialkoXy-benzene residue while the other is anaphthalene sulfonic acld residue or wherein both R and R aredialkoXybenzene residues; and wherein R stands for an acyl group; saiddyestufiis being dark powders, soluble in water with a bluish-vioinwhich one B is an SO H group while the acyl group.

let color, and in sulfuric acid with a greenish-blue color; and saiddyestuifs dyeing cotton directly in blue to bluish gray to gray shades.

7. As new products of manufacture, dyestuffs having the followingprobable general formula:

O-alkyl stuff, theste which comprises diazotizing a compoundthefollowing probable general formula:

in which R, is an aryl residue of the benzene or naphthalene serieswhich may be further substituted by alkyl, halogen, alkoxy or sulfonicacid groups but which contains no hydroxyl groups, and in which one ofthe members R and R is a dialkoxy benzene residue while the other is anaphthalene sulfonic acid residue orin which both R and R aredialkoXy-benzene residues, and couplingto a compound of the followingprobable general formula? i whichR is an acyl group. 11. ,As newproducts ofmanufacture dyein which R stands for a residue of the benzeneor naphthalene series which contains no OH groups, and in which R standsfor an 8. As new products of manufacture, dyestuffs having the followinggeneral formula:

OOH: f

=: wherein R stands for a residuevof the henzene or naphthalene serieswhich contains no OH groups.

9. As a new product of manufacture, a dyestuff having the followinggeneral forother H is a hydrogen atom, said dyestuffs being dark powderssoluble in water with a bluish-violet color and in sulfuric acid with agreenish-blue color, and said dyestuffs dyeing cotton directly inbluish-gray shades of good fastness to light.

10. In the process of preparing an azo dyestuffs having the followinggeneral formula: 1. ----w.on"

wherein R is an aryl residue of the benzene or naphthalene series whichmay be further substituted by alkyl, halogen, alkoxy or sulfonic acidgroups, but which contains no OH group; wherein one of the members R andR is a dialkoxy-benzene residue while the H N H-C 0-011:

other is a naphthalene sulfonic acid residue or wherein both R and R aredialkoxy-benzene residues; and wherein R stands for an acyl group; saiddyestuffs being dark powders, soluble in water with a bluish-violetcolor, and in sulphuric acid with a greenishblue color; and saiddyestuffs dyeing cotton directly in blue to bluish-gray to gray shades.1;

112, insn wgpmduct cifrmanuf-a tnr rdyeistufi sharing:th ifollnwingepr bbl ;geuem O alkyl in which R1: stands for a. residue of therben-,czreneornaphthalene series which-may be further substituted by-alkyl,halogen, alkoxy or sulfonic acid groups but which contains no OH groups,and in which R stands foran acyl group.

13. As new products of manufacture, dyestuifs having the followinggeneral formula:

OCH! OH wherein R stands for a residue of the benzene or naphthaleneseries which may begfurther substituted by alkyl, halogen, alkoxyorsulfonic acid groups but which contains no 1 @Hgroup.

In testimony whereof, we have hereunto subscribed our names atCarrollville, Milwaukee';County,Wisconsin.

-' I,V A N GUBELMANN.

, ARTHUR R. MURPHY.

